Composition including a glycerol ester including at least two epoxides for treatment of subterranean formations

ABSTRACT

Various embodiments disclosed relate to compositions including a glycerol ester including at least two epoxides for treatment of subterranean formations. In various embodiments, the present invention provides a method of treating a subterranean formation. The method includes placing in a subterranean formation a composition including a glycerol ester that includes at least two epoxides. The composition also includes a hardening agent.

BACKGROUND

The presence of particulate matter, such as sand, in produced fluids from hydrocarbon wells can be problematic. For example, particulates can abrade pumping and other production equipment and reduce the fluid production capabilities of the producing zones. Hydrocarbon wells are often located in subterranean zones that contain unconsolidated particulate matter that can migrate out of the well along with oil, gas, water, or other fluids produced by the well. Placing proppant downhole during hydraulic fracturing operations can result in unconsolidated proppant that can become entrained with produced fluids.

Sand or proppant consolidation is one of the most convenient and cost effective methods to avoid production of these particulates, such as using curable resins. However, many curable resins, such as many epoxy- and formaldehyde-based resins, can have negative effects on health and the environment.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

FIG. 1 illustrates a system or apparatus for delivering a composition to a subterranean formation, in accordance with various embodiments.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. A comma can be used as a delimiter or digit group separator to the left or right of a decimal mark; for example, “0.000,1” is equivalent to “0.0001.”

In the methods of manufacturing described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, within 1%, or within 0% of a stated value or of a stated limit of a range.

The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “organic group” as used herein refers to but is not limited to any carbon-containing functional group. For example, an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group, a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R)₂, CN, CF₃, OCF₃, R, C(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R, wherein R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can itself be further substituted.

The term “substituted” as used herein refers to an organic group as defined herein or molecule in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The term “functional group” or “substituent” as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents J that can be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R)₂, CN, NO, NO₂, ONO₂, azido, CF₃, OCF₃, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl.

The term “alkyl” as used herein refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl. Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

The term “alkenyl” as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to vinyl, —CH═CH(CH₃), —CH═C(CH₃)₂, —C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among others.

The term “acyl” as used herein refers to a group containing a carbonyl moiety wherein the group is bonded via the carbonyl carbon atom. The carbonyl carbon atom is also bonded to another carbon atom, which can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group or the like. In the special case wherein the carbonyl carbon atom is bonded to a hydrogen, the group is a “formyl” group, an acyl group as the term is defined herein. An acyl group can include 0 to about 12-20 or 12-40 additional carbon atoms bonded to the carbonyl group. An acyl group can include double or triple bonds within the meaning herein. An acryloyl group is an example of an acyl group. An acyl group can also include heteroatoms within the meaning here. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When the group containing the carbon atom that is bonded to the carbonyl carbon atom contains a halogen, the group is termed a “haloacyl” group. An example is a trifluoroacetyl group.

The term “aryl” as used herein refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups. Aryl groups can be unsubstituted or substituted, as defined herein. Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substituted naphthyl groups, which can be substituted with carbon or non-carbon groups such as those listed herein.

The term “heterocyclyl” as used herein refers to aromatic and non-aromatic ring compounds containing three or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S. The term “alkoxy” as used herein refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined herein. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can include one to about 12-20 or about 12-40 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms. For example, an allyloxy group is an alkoxy group within the meaning herein. A methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structure are substituted therewith.

The term “amine” as used herein refers to primary, secondary, and tertiary amines having, e.g., the formula N(group)₃ wherein each group can independently be H or non-H, such as alkyl, aryl, and the like. Amines include but are not limited to R—NH₂, for example, alkylamines, arylamines, alkylarylamines; R₂NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and R₃N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like. The term “amine” also includes ammonium ions as used herein.

The term “amino group” as used herein refers to a substituent of the form —NH₂, —NHR, —NR₂, —NR₃ ⁺, wherein each R is independently selected, and protonated forms of each, except for —NR₃ ⁺, which cannot be protonated. Accordingly, any compound substituted with an amino group can be viewed as an amine. An “amino group” within the meaning herein can be a primary, secondary, tertiary, or quaternary amino group. An “alkylamino” group includes a monoalkylamino, dialkylamino, and trialkylamino group.

The terms “halo,” “halogen,” or “halide” group, as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

The term “haloalkyl” group, as used herein, includes mono-halo alkyl groups, poly-halo alkyl groups wherein all halo atoms can be the same or different, and per-halo alkyl groups, wherein all hydrogen atoms are replaced by halogen atoms, such as fluoro. Examples of haloalkyl include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

The term “hydrocarbon” as used herein refers to a functional group or molecule that includes carbon and hydrogen atoms. The term can also refer to a functional group or molecule that normally includes both carbon and hydrogen atoms but wherein all the hydrogen atoms are substituted with other functional groups.

As used herein, the term “hydrocarbyl” refers to a functional group derived from a straight chain, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof.

The term “solvent” as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

The term “room temperature” as used herein refers to a temperature of about 15° C. to 28° C.

The term “standard temperature and pressure” as used herein refers to 20° C. and 101 kPa.

As used herein, “degree of polymerization” is the number of repeating units in a polymer.

As used herein, the term “polymer” refers to a molecule having at least one repeating unit and can include copolymers.

The term “copolymer” as used herein refers to a polymer that includes at least two different repeating units. A copolymer can include any suitable number of repeating units.

The term “downhole” as used herein refers to under the surface of the earth, such as a location within or fluidly connected to a wellbore.

As used herein, the term “drilling fluid” refers to fluids, slurries, or muds used in drilling operations downhole, such as during the formation of the wellbore.

As used herein, the term “stimulation fluid” refers to fluids or slurries used downhole during stimulation activities of the well that can increase the production of a well, including perforation activities. In some examples, a stimulation fluid can include a fracturing fluid or an acidizing fluid.

As used herein, the term “clean-up fluid” refers to fluids or slurries used downhole during clean-up activities of the well, such as any treatment to remove material obstructing the flow of desired material from the subterranean formation. In one example, a clean-up fluid can be an acidification treatment to remove material formed by one or more perforation treatments. In another example, a clean-up fluid can be used to remove a filter cake.

As used herein, the term “fracturing fluid” refers to fluids or slurries used downhole during fracturing operations.

As used herein, the term “spotting fluid” refers to fluids or slurries used downhole during spotting operations, and can be any fluid designed for localized treatment of a downhole region. In one example, a spotting fluid can include a lost circulation material for treatment of a specific section of the wellbore, such as to seal off fractures in the wellbore and prevent sag. In another example, a spotting fluid can include a water control material. In some examples, a spotting fluid can be designed to free a stuck piece of drilling or extraction equipment, can reduce torque and drag with drilling lubricants, prevent differential sticking, promote wellbore stability, and can help to control mud weight.

As used herein, the term “completion fluid” refers to fluids or slurries used downhole during the completion phase of a well, including cementing compositions.

As used herein, the term “remedial treatment fluid” refers to fluids or slurries used downhole for remedial treatment of a well. Remedial treatments can include treatments designed to increase or maintain the production rate of a well, such as stimulation or clean-up treatments.

As used herein, the term “abandonment fluid” refers to fluids or slurries used downhole during or preceding the abandonment phase of a well.

As used herein, the term “acidizing fluid” refers to fluids or slurries used downhole during acidizing treatments. In one example, an acidizing fluid is used in a clean-up operation to remove material obstructing the flow of desired material, such as material formed during a perforation operation. In some examples, an acidizing fluid can be used for damage removal.

As used herein, the term “cementing fluid” refers to fluids or slurries used during cementing operations of a well. For example, a cementing fluid can include an aqueous mixture including at least one of cement and cement kiln dust. In another example, a cementing fluid can include a curable resinous material such as a polymer that is in an at least partially uncured state.

As used herein, the term “water control material” refers to a solid or liquid material that interacts with aqueous material downhole, such that hydrophobic material can more easily travel to the surface and such that hydrophilic material (including water) can less easily travel to the surface. A water control material can be used to treat a well to cause the proportion of water produced to decrease and to cause the proportion of hydrocarbons produced to increase, such as by selectively binding together material between water-producing subterranean formations and the wellbore while still allowing hydrocarbon-producing formations to maintain output.

As used herein, the term “packer fluid” refers to fluids or slurries that can be placed in the annular region of a well between tubing and outer casing above a packer. In various examples, the packer fluid can provide hydrostatic pressure in order to lower differential pressure across the sealing element, lower differential pressure on the wellbore and casing to prevent collapse, and protect metals and elastomers from corrosion.

As used herein, the term “fluid” refers to liquids and gels, unless otherwise indicated.

As used herein, the term “subterranean material” or “subterranean formation” refers to any material under the surface of the earth, including under the surface of the bottom of the ocean. For example, a subterranean formation or material can be any section of a wellbore and any section of a subterranean petroleum- or water-producing formation or region in fluid contact with the wellbore. Placing a material in a subterranean formation can include contacting the material with any section of a wellbore or with any subterranean region in fluid contact therewith. Subterranean materials can include any materials placed into the wellbore such as cement, drill shafts, liners, tubing, casing, or screens; placing a material in a subterranean formation can include contacting with such subterranean materials. In some examples, a subterranean formation or material can be any below-ground region that can produce liquid or gaseous petroleum materials, water, or any section below-ground in fluid contact therewith. For example, a subterranean formation or material can be at least one of an area desired to be fractured, a fracture or an area surrounding a fracture, and a flow pathway or an area surrounding a flow pathway, wherein a fracture or a flow pathway can be optionally fluidly connected to a subterranean petroleum- or water-producing region, directly or through one or more fractures or flow pathways.

As used herein, “treatment of a subterranean formation” can include any activity directed to extraction of water or petroleum materials from a subterranean petroleum- or water-producing formation or region, for example, including drilling, stimulation, hydraulic fracturing, clean-up, acidizing, completion, cementing, remedial treatment, abandonment, and the like.

As used herein, a “flow pathway” downhole can include any suitable subterranean flow pathway through which two subterranean locations are in fluid connection. The flow pathway can be sufficient for petroleum or water to flow from one subterranean location to the wellbore or vice-versa. A flow pathway can include at least one of a hydraulic fracture, and a fluid connection across a screen, across gravel pack, across proppant, including across resin-bonded proppant or proppant deposited in a fracture, and across sand. A flow pathway can include a natural subterranean passageway through which fluids can flow. In some embodiments, a flow pathway can be a water source and can include water. In some embodiments, a flow pathway can be a petroleum source and can include petroleum. In some embodiments, a flow pathway can be sufficient to divert from a wellbore, fracture, or flow pathway connected thereto at least one of water, a downhole fluid, or a produced hydrocarbon.

As used herein, a “carrier fluid” refers to any suitable fluid for suspending, dissolving, mixing, or emulsifying with one or more materials to form a composition. For example, the carrier fluid can be at least one of crude oil, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, butylglycidyl ether, propylene carbonate, D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester (e.g., a fatty acid methyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxy ethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethyl sulfoxide, dimethyl formamide, a petroleum distillation product of fraction (e.g., diesel, kerosene, napthas, and the like) mineral oil, a hydrocarbon oil, a hydrocarbon including an aromatic carbon-carbon bond (e.g., benzene, toluene), a hydrocarbon including an alpha olefin, xylenes, an ionic liquid, methyl ethyl ketone, an ester of oxalic, maleic or succinic acid, methanol, ethanol, propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), an aliphatic hydrocarbon (e.g., cyclohexanone, hexane), water, brine, produced water, flowback water, brackish water, and sea water. The fluid can form about 0.001 wt % to about 99.999 wt % of a composition, or a mixture including the same, or about 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more.

In various embodiments, the present invention provides a method of treating a subterranean formation. The method includes placing in a subterranean formation a composition including a glycerol ester including at least two epoxides. The composition also includes a hardening agent.

In various embodiments, the present invention provides a method of treating a subterranean formation. The method includes placing in a subterranean formation a composition including a glycerol ester including at least two epoxides having the structure:

The variables R¹, R², and R³ are independently chosen from —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl. In at least one of R¹, R², and R³, the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl each independently include about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of R¹, R², and R³, the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl (e.g., including 2-30 epoxide groups). The composition also includes an amine-functional hardening agent.

In various embodiments, the present invention provides a system including a composition that includes a glycerol ester including at least two epoxides. The composition also includes a hardening agent. The system also includes a subterranean formation including the composition therein.

In various embodiments, the present invention provides a composition for treatment of a subterranean formation. The composition includes a glycerol ester including at least two epoxides. The composition also includes a hardening agent.

In various embodiments, the present invention provides a method of preparing a composition for treatment of a subterranean formation. The method includes forming a composition including a glycerol ester including at least two epoxides. The composition also includes a hardening agent.

Various embodiments of the present invention provide certain advantages over other compositions and methods for consolidation, at least some of which are unexpected. In some embodiments, the composition can be more environmentally friendly than other curable compositions. In some embodiments, the epoxide-containing glycerol ester and the hardening agent can be free of aromatic groups and therefore less toxic than other aromatic group-containing compositions. In some embodiments, the epoxide-containing glycerol ester can be derived from more environmentally friendly sources than other materials, such as from oils like vegetable oils. In some embodiments, its greater environmental friendliness makes the composition easier to use in areas having strict environmental regulations, including, in some examples, use of more liberal quantities of the composition.

In various embodiments, the composition can be less expensive than other consolidating compositions, providing a greater amount of consolidation for a given cost than other consolidating compositions. In some embodiments, the epoxide-containing glycerol ester can be derived from cheaper and more renewable resources than other consolidating resins, such as oils like vegetable oils. In various embodiments, the composition can cause less damage to the formation than other curable compositions. In some embodiments, by providing a greater regain permeability, higher production rates can be achieved.

In various embodiments, the composition can form a stronger bond with proppants, gravel, and subterranean surfaces than other consolidating compositions, providing greater strength using a smaller amount of curable composition as compared to other treatment methods. In some embodiments, a free hydroxy group can increase bonding strength to particulate or subterranean surfaces over other curable compositions. In some embodiments, a more permeable consolidated material can be formed having the same or greater strength than a consolidated material formed using a larger amount of another curable composition. In various embodiments, by using a smaller amount of curable composition, the composition can provide greater regain permeability than other consolidating methods that provide similar strength but require larger amounts of resin. In some embodiments, since a smaller amount of curable composition is required, a consolidation treatment using the composition can proceed more quickly than other consolidation treatments.

Other curable compositions employ a solvent to dilute the composition and provide lower viscosity, reducing the concentration of the curable materials and providing reduced consolidating strength. In various embodiments, the epoxide-containing glycerol ester can act as a reactive diluent, providing reduced viscosity to the uncured composition using less or no diluting solvent, providing a composition suitable for pumping into subterranean formations having lower permeabilities. In various embodiments, the lower viscosity of the composition including the epoxide-containing glycerol ester can enable better penetration into the subterranean formation and can provide better consolidation not only in the near wellbore region but also deeper in the formation. In various embodiments, by acting as a reactive diluent, the epoxide-containing glycerol ester provides dilution and viscosity decrease without reducing the effective concentration of the epoxide-containing glycerol ester, allowing a high degree of consolidation even in formations with lower permeabilities or higher fines content.

In various embodiments, the epoxide-containing glycerol ester can be used in combination with other curable resins, such as other epoxide resins. In various embodiments, the composition including the epoxide-containing glycerol ester can provide good consolidation strength without decreasing or with only a minor decrease in permeability of formations that include large amounts of fines and clays. In various embodiments, the composition including the epoxide-containing glycerol ester can have a higher flash point than other consolidation compositions. In various embodiments, a proppant or gravel coated with a cured reaction product of the epoxide-containing glycerol ester and hardening agent can have enhanced strength and crush resistance compared to a corresponding proppant or gravel that is free of the coating.

Method of Treating a Subterranean Formation.

In some embodiments, the present invention provides a method of treating a subterranean formation. The method includes placing in a subterranean formation a composition including an epoxide-containing glycerol ester and a hardening agent. The composition can be or can include a consolidating resin. In various embodiments, the composition can be used in well completion operations, such as primary proppant treatments for immobilizing proppant particulates (e.g., hydraulic fracturing, gravel packing, and frac-packing), remedial proppant/gravel treatments, near-wellbore formation sand consolidation treatments for sand control, consolidating-while-drilling target intervals, and plugging-and-abandonment of wellbores in subterranean formations. In some embodiments, the composition includes the epoxide-containing glycerol ester and hardening agent used as a reactive diluent, such as in a composition including other hardenable resins (e.g., epoxy resins or other resins) or in a composition only including the glycerol ester and the hardening agent as the hardenable components of the composition. In some embodiments, the composition can include the epoxide-containing glycerol ester and hardening agent or a cured reaction product thereof as a coating on a proppant (e.g., sand) or on gravel. In various embodiments, a proppant or gravel coated with a cured reaction product of the epoxide-containing glycerol ester and hardening agent can have enhanced strength and crush resistance compared to a corresponding proppant or gravel that is free of the coating.

The method can include obtaining or providing the composition (e.g., mixing the epoxide-containing glycerol ester and the hardening agent, or mixing other components to form the composition). The obtaining or providing of the composition can occur at any suitable time and at any suitable location. The obtaining or providing of the composition can occur above the surface. The obtaining or providing of the composition can occur in the subterranean formation (e.g., downhole). The method also includes placing the composition in a subterranean formation. The placing of the composition in the subterranean formation can include contacting the composition and any suitable part of the subterranean formation, or contacting the composition and a subterranean material, such as any suitable subterranean material. The subterranean formation can be any suitable subterranean formation. In some examples, the placing of the composition in the subterranean formation includes contacting the composition with or placing the composition in at least one of a fracture, at least a part of an area surrounding a fracture, a flow pathway, an area surrounding a flow pathway, and an area desired to be fractured. The placing of the composition in the subterranean formation can be any suitable placing and can include any suitable contacting between the subterranean formation and the composition. The placing of the composition in the subterranean formation can include at least partially depositing the composition in a fracture, flow pathway, or area surrounding the same.

The method can include hydraulic fracturing, such as a method of hydraulic fracturing to generate a fracture or flow pathway. The placing of the composition in the subterranean formation or the contacting of the subterranean formation and the hydraulic fracturing can occur at any time with respect to one another; for example, the hydraulic fracturing can occur at least one of before, during, and after the contacting or placing. In some embodiments, the contacting or placing occurs during the hydraulic fracturing, such as during any suitable stage of the hydraulic fracturing, such as during at least one of a pre-pad stage (e.g., during injection of water with no proppant, and additionally optionally mid- to low-strength acid), a pad stage (e.g., during injection of fluid only with no proppant, with some viscosifier, such as to begin to break into an area and initiate fractures to produce sufficient penetration and width to allow proppant-laden later stages to enter), or a slurry stage of the fracturing (e.g., viscous fluid with proppant). The method can include performing a stimulation treatment at least one of before, during, and after placing the composition in the subterranean formation in the fracture, flow pathway, or area surrounding the same. The stimulation treatment can be, for example, at least one of perforating, acidizing, injecting of cleaning fluids, propellant stimulation, and hydraulic fracturing. In some embodiments, the stimulation treatment at least partially generates a fracture or flow pathway where the composition is placed or contacted, or the composition is placed or contacted to an area surrounding the generated fracture or flow pathway.

The method can include at least partially curing the composition, to form a cured product of the composition. In some embodiments, substantially all of the composition is curable, while in other embodiments the composition includes curable components and non-curable components such that only part of the composition is curable. For example, in some embodiments, the composition includes a slurry of proppant particles in a carrier fluid, wherein the proppant particles are coated with curable components but the carrier fluid is substantially non-curable. The curable components of the composition can be a curable resin. In some embodiments, the curable components of the composition can be about 0.001 wt % to about 99.999 wt % of the composition, or about 0.1 wt % to about 80 wt %, or about 1 wt % to about 50 wt %, or about 1 wt % or more of the composition, or about 2 wt %, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt % or more. In some embodiments, the curing can include curing about 1 wt % or more of the curable components, or about 2 wt %, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt % or more of the curable components of the composition. The curing can occur at any suitable location, such as at the surface, during transport downhole, at a downhole location, or a combination thereof. In some embodiments, the composition is allowed to react at least partially above the surface with a gravel or proppant surface to form bonds thereto (e.g., in an embodiment wherein the epoxide-containing glycerol ester includes a free hydroxy group, via hydroxy-reactive silicon groups such as alkoxy- or hydroxy-substituted silanes), and the composition is allowed to cure downhole. In some embodiments, reaction with the surface of gravel, proppant, or the subterranean formation can occur at least partially downhole. The curing can be initiated by any suitable conditions, such as pressure, temperature, or by presence of a chemical catalyst or initiator. In some embodiments, the composition can include a base, such as any suitable organic or inorganic base, such as triethylamine, to catalyze the curing process.

Any suitable proportion of the composition can be one or more downhole fluids or one or more carrier liquids. In some embodiments about 0.001 wt % to about 99.999 wt % of the composition can be a downhole fluid or carrier liquid, or about 0.1 wt % to about 80 wt %, or about 1 wt % to about 50 wt %, or about 1 wt % or more of the composition, or about 2 wt %, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt % or more.

In various embodiments, the composition, a cured product thereof, or mixture including the composition or a cured product thereof can include a proppant or gravel. A proppant is a material that keeps an induced hydraulic fracture at least partially open during or after a fracturing treatment. Proppants can be transported into the subterranean formation (e.g., downhole) to the fracture using fluid, such as fracturing fluid or another fluid. A higher-viscosity fluid can more effectively transport proppants to a desired location in a fracture, especially larger proppants, by more effectively keeping proppants in a suspended state within the fluid. Examples of proppants can include sand, gravel, glass beads, polymer beads, ground products from shells and seeds such as walnut hulls, and manmade materials such as ceramic proppant, bauxite, tetrafluoroethylene materials (e.g., TEFLON™ available from DuPont), fruit pit materials, processed wood, composite particulates prepared from a binder and fine grade particulates such as silica, alumina, fumed silica, carbon black, graphite, mica, titanium dioxide, meta-silicate, calcium silicate, kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, and solid glass, or mixtures thereof. In some embodiments, the proppant can have an average particle size, wherein particle size is the largest dimension of a particle, of about 0.001 mm to about 3 mm, about 0.15 mm to about 2.5 mm, about 0.25 mm to about 0.43 mm, about 0.43 mm to about 0.85 mm, about 0.85 mm to about 1.18 mm, about 1.18 mm to about 1.70 mm, or about 1.70 to about 2.36 mm. In some embodiments, the proppant can have a distribution of particle sizes clustering around multiple averages, such as one, two, three, or four different average particle sizes. The composition or mixture can include any suitable amount of proppant or gravel, such as about 0.01 wt % to about 99.99 wt %, about 1 wt % to about 90 wt %, about 5 wt % to about 70 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, about 99.9 wt %, or about 99.99 wt % or more. In some embodiments, the composition includes curable components (e.g., the epoxide-containing glycerol ester and a hardening agent, and any other optional curable components) at least partially coated on the proppant or gravel. In some embodiments, the curable components of the composition can form or be part of a liquid that suspends the proppant in a slurry.

In various embodiments, the composition includes the epoxide-containing glycerol ester and the hardening agent, a silane coupling agent, a surfactant for facilitating the coating of the curable components on particulate substrates, and a carrier fluid.

In one embodiment, a method of treating proppant on the fly during the hydraulic fracturing treatment or screenless frac-pack treatment can include: mixing components of the composition together to form a single, homogenous mixture; coating the mixture on the proppant while the proppant is being mixed in a fracturing carrier fluid; injecting the resin-treated proppant slurry into a wellbore to be placed in a generated fracture located in the subterranean formation; allowing the system to cure at formation temperature.

In another embodiment, a method of treating the formation with the composition includes: mixing components of the composition together in a soluble solvent; injecting the mixture into the formation interval that requires treatment; postflushing with a solvent or a gas; allowing the system to cure at formation temperature

In one embodiment, the present invention provides a method of treating proppant using a wet coat or on the fly method, such as during a hydraulic fracturing treatment. In another embodiment, the present invention provides a method of dry coating or pretreating the proppant prior to a fracturing treatment, generally including applying a mixture of the epoxide-containing glycerol ester and the hardening agent, and any other optional components of the composition, to the dry proppant.

The method can further include applying a preflush solution to the subterranean formation. The preflush solution can be any suitable preflush solution. For example, the preflush solution can ready the subterranean material to receive the composition and can remove oils that can impede the composition from making contact with particulates that are desired to be consolidated by the composition. The preflush solution can include an aqueous liquid. The aqueous liquid in the preflush solution can include at least one of salt water and brine. The preflush solution can include a surfactant. The surfactant in the preflush solution can include at least one of an ethoxylated nonyl phenol phosphate ester, a cationic surfactant, a non-ionic surfactant, an alkyl phosphonate surfactant, or mixtures thereof.

The method can further include applying an afterflush fluid to the subterranean formation. For example, the afterflush fluid can displace the composition from selected areas of the wellbore to remove the composition from the pore spaces inside the subterranean formation and thereby restore permeability while leaving behind composition at, for example, contact points between the subterranean formation and particulates such that the particulates can be consolidated. The afterflush fluid can be any suitable afterflush fluid, such as at least one of salt water, brine, and nitrogen gas.

Epoxide-Containing Glycerol Ester.

The composition includes a glycerol ester that includes at least two epoxide groups. The composition can include one or more glycerol esters that include at least two epoxide groups. The epoxide-containing glycerol ester can be present in the composition in any suitable concentration, such that the composition can be used as described herein. For example, the one or more epoxide-containing glycerol esters can be about 0.001 wt % to about 50 wt % of the composition, about 0.01 wt % to about 30 wt % of the composition, about 0.001 wt % or less, about 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, or about 50 wt % or more of the composition.

The epoxide-containing glycerol ester can be any suitable ester of glycerol. The glycerol ester can be at least one of a mono-, di-, or tri-glyceride (e.g., having two, one, or zero free hydroxy groups on the glycerol, respectively). The glycerol esters can be fatty acid (e.g., C₅-C₆₀) glycerol esters.

In some embodiments, the glycerol ester including at least two epoxides has the following structure:

The variables R¹, R², and R³ can be independently chosen from —H, substituted or unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴. The variable R⁴ at each occurrence can be independently —C(O)—(C₂-C₆₀)hydrocarbyl including at least two oxygen atoms each independently directly attached to two different adjacent carbon atoms of the (C₂-C₆₀)hydrocarbyl. The (C₁-C₆₀)hydrocarbyl and the (C₂-C₆₀)hydrocarbyl can be independently interrupted by 0, 1, 2, or 3 groups independently chosen from —O—, —S—, and substituted or unsubstituted —NH—. At least one of R¹, R², and R³ can be R⁴.

The variables R¹, R², and R³ can be independently chosen from —H, substituted or unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴. In some embodiments, each of R¹, R², and R³ are independently selected from R⁴ and —H. In some embodiments, at least two of R¹, R², and R³ are R⁴. In some embodiments, each of R¹, R², and R³ is R⁴. In some embodiments, R¹, R², and R³ are independently chosen from —H, substituted or unsubstituted (C₅-C₆₀)alkyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkyl substituted or unsubstituted (C₅-C₆₀)alkenyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkenyl, and R⁴. The (C₅-C₆₀)alkenyl and the —C(O)—(C₄-C₅₉)alkenyl can each independently include about 1 to about 29 carbon-carbon double bonds (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29). The (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenyl can each independently include about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenyl (e.g., including 2-30 epoxide groups). In some embodiments, R⁴ at each occurrence is independently chosen from —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl. The (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl can each independently include about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of the (C₂-C₆₀)alkyl or the (C₂-C₆₀)alkenyl (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 epoxide groups). As used herein “adjacent carbon atoms” are carbon atoms that are directly bound to one another.

In some embodiments, the glycerol ester including at least two epoxides is an oil including at least one epoxidized aliphatic carbon-carbon double bond. For example, the glycerol ester including at least two epoxides can be an oil that has been epoxidized (e.g., wherein at least one aliphatic carbon-carbon double bond has been epoxidized). The oil can be açai oil, almond oil, amaranth oil, apple seed oil, apricot oil, argan oil, avocado oil, babassu oil, beech nut oil, ben oil, bitter gourd oil (from the seeds of Momordica charantia), black seed oil, blackcurrant seed oil (from the seeds of Ribes nigrum), borage seed oil (from the seeds of Borago officinalis), borneo tallow nut oil, bottle gourd oil (from the seeds of the Lagenaria siceraria), buffalo gourd oil (from the seeds of the Cucurbita foetidissima), butternut squash seed oil (from the seeds of Cucurbita moschata), camelina sativa oil, cape chestnut oil (yangu oil), carob pod oil, cashew oil, cocklebur oil, cocoa butter, coconut oil, cohune oil, coriander seed oil, corn oil, cottonseed oil, date seed oil, dika oil, egusi seed oil (from the seeds of Cucumeropsis mannii naudin), evening primrose oil (from the seeds of Oenothera biennis), flaxseed oil (from the seeds of Linum usitatissimum), grape seed oil, grapefruit seed oil, hazelnut oil, hemp oil, kapok seed oil, kenaf seed oil (from the seeds of Hibiscus cannabinus), lallemantia oil (from the seeds of Lallemantia iberica), linseed oil, macadamia oil, mafura oil (from the seeds of Trichilia emetic), manila oil (from the kernel of Sclerocarya birrea), meadowfoam seed oil, mongongo nut oil (manketti oil), mustard oil, niger seed oil, okra seed oil, olive oil, orange oil, palm oil, papaya seed oil, peanut oil, pecan oil, pequi oil (from the seeds of Caryocar brasiliense), perilla seed oil, persimmon seed oil (from the seeds of Diospyros virginiana), pili nut oil (from the seeds of Canarium ovatum), pistachio oil, pomegranate seed oil, poppyseed oil, prune kernel oil, pumpkin seed oil, quinoa oil, ramtil oil (from Guizotia abyssinica, the Niger pea), rapeseed oil, rice bran oil, royle oil (from the seeds of Prinsepia utilis), safflower oil, sapote oil, seje oil (from the seeds of Jessenia bataua), sesame oil, shea butter, soybean oil, sunflower oil, taramira oil, tea seed oil (Camellia oil), thistle oil, tigernut oil (or nut-sedge oil), tobacco seed oil, tomato seed oil, walnut oil, watermelon seed oil, wheat germ oil, one or more fractions thereof (e.g., one or more components of the oil), or a combination thereof. In some embodiments, the oil can be chosen from agarwood oil, allspice oil, almond oil, anise oil, basil oil, bay leaf oil, benzoin oil, bergamot oil, buchu oil, camphor oil, cannabis oil, cassia oil, cedar oil, celery oil, chamomile oil, cinnamon oil, clary sage oil, clove oil, copaiba oil, cumin oil, eucalyptus oil, frankincense oil, galangal oil, geranium oil, ginger oil, grapefruit oil, guava oil, hops oil, hyssop oil, jasmine oil, juniper oil, lavender oil, lemon grass oil, lemon oil, lemongrass oil, lime oil, manuka oil, mandarin orange, marjoram oil, melaleuca oil, myrrh oil, nutmeg oil, orange oil, oregano oil, patchouli oil, peppermint oil, pine oil, rose oil, rosehip oil, rosemary oil, rosewood oil, sage oil, sandalwood oil, sassafras oil, spearmint oil, tangerine oil, tea tree oil, thyme oil, tsuga oil, valerian oil, vanilla oil, wintergreen oil, ylang-ylang oil, one or more fractions thereof (e.g., one or more components of the oil), or a combination thereof. In some embodiments, the oil can be chosen from soybean oil, linseed oil, a fraction thereof, and combinations thereof.

In some embodiments, the glycerol ester including at least two epoxides can have the structure:

In some embodiments, the glycerol ester including at least two epoxides can have the structure:

The glycerol ester including at least two epoxides can have any suitable epoxide equivalent weight (e.g., the grams of the glycerol ester needed to provide 1 mole of epoxide functionalities) consistent with the structures described herein. For example, the epoxide-containing glycerol ester can have an epoxide equivalent weight of about 50 g/mol to about 1,000 g/mol, or about 100 g/mol to about 500 g/mol, or about 150 g/mol to about 300 g/mol, or about 50 g/mol or less, or about 75 g/mol, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or about 1,000 g/mol or more.

Hardening Agent.

The hardening agent can be any suitable hardening agent that can react with the epoxide-containing glycerol ester to form a cured product thereof that is effective for consolidation. The hardening agent can be an epoxide-reactive hardening agent. The hardening agent can include a nucleophilic group that can attack and open an epoxide, such as a primary or secondary amine. The hardening agent can be an amine-functional hardening agent, and can include at least one of an amine, an aromatic amine, an aliphatic amine, a cyclo-aliphatic amine, a polyamine, an amide, and a polyamide. The hardening agent can be selected from the group consisting of diethylene tetramine, ethylene diamine, polyethyleneimine, piperidine, triethylamine, benzyldimethylamine, N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, piperazine, aminoethylpiperazine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, carbazole, carbazole, phenanthridine, acridine, phenathroline, phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, indoline, isoindoline, quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole, polyethyleneimine, 2-ethyl-4-methyl imidazole, 1,1,3-trichlorotrifluoroacetone, a substituted or unsubstituted derivative of any one thereof, and combinations thereof.

In some embodiments, the hardening agent can include an amine-containing polymer. In some embodiments, the hardening agent can be hydrophobically-modified. In some embodiments, the hardening agent can include at least one of a polyamine (e.g., spermidine and spermine), a polyimine (e.g., poly(ethylene imine) and poly(propylene imine)), a polyamide, poly(2-(N,N-dimethylamino)ethyl methacrylate), poly(2-(N,N-diethylamino)ethyl methacrylate), poly(vinyl imidazole), and a copolymer including monomers of at least one of the foregoing and monomers of at least one non-amine-containing polymer such as of at least one of polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylpyridine, polyacrylic acid, polyacrylate, and polymethacrylate. The hydrophobic modification can be any suitable hydrophobic modification, such as at least one (C₄-C₃₀)hydrocarbyl including at least one of a straight chain, a branched chain, an unsaturated C—C bond, an aryl group, and any combination thereof.

The hardening agent can include at least one amine component that is a polyamine-substituted (C₁-C₃₀)hydrocarbyl, whererein the (C₁-C₃₀)hydrocarbyl and each amine are independently substituted or unsubstituted, in any suitable proportion of the composition, such as about 5 wt % to about 50 wt %, about 10 wt % to about 30 wt %, about 5 wt % or less, or about 10 wt %, 15, 20, 25, 30, 35, 40, 45, or about 50 wt % or more. The hardening agent can be a bis(amino(C₀-C₅)hydrocarbyl)(C₆-C₂₀)aryl compound, wherein the (C₆-C₂₀)aryl, (C₀-C₅)hydrocarbyl, and each amine are each independently substituted or unsubstituted. The amine component can be diethyltoluenediamine. The hardening agent can include at least one amine component that is a polyamine-substituted poly((C₂-C₅)hydrocarbyloxy), wherein each (C₂-C₅)hydrocarbyloxy and each amine are independently substituted or unsubstituted. The hardening agent can be polyoxypropylene diamine. The hardening agent can include an amine component that is a mono- or polyamino(C₀-C₁₀)hydrocarbyl(C₆-C₂₀)aryl compound, wherein the (C₀-C₁₀)hydrocarbyl, (C₆-C₂₀)aryl, and each amine are each independently substituted or unsubstituted. The hardening agent can be a tris(amino(C₁-C₃)hydrocarbyl)benzene, wherein the (C₁-C₃)hydrocarbyl, the benzene, and each amine are independently substituted or unsubstituted. The amine component can be 2,4,6-tris(dimethylaminomethyl)phenol.

Other Components.

The composition including the epoxide-containing glycerol ester and the hardening agent, a mixture including the composition, or a cured product thereof, can include any suitable additional component in any suitable proportion, such that the composition, mixture including the same, or cured product thereof, can be used as described herein.

In some embodiments, the composition or a cured product thereof further includes a silane coupling agent. The silane coupling agent can be any suitable silane coupling agent. For example, the silane coupling agent can be a (C₁-C₃₀)hydrocarbyl-substituted trimethoxysilane, wherein the hydrocarbyl group is substituted or unsubstituted. The silane coupling agent can be N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane. Any suitable amount of the composition or a cured product thereof can be the silane coupling agent, such as about 0.001 wt % to about 20 wt %, or about 0.001 wt % to about 3 wt %, or about 0.001 wt % or less, or about 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or about 20 wt % or more.

The composition or a cured product thereof can include one or more surfactants. The surfactant can facilitate the coating of the curable components of the composition on proppant, gravel, or a subterranean surface causing the curable components to flow to the contact points between adjacent proppant particles. The surfactant can be any suitable surfactant, such that the composition can be used as described herein. The surfactant can form any suitable proportion of the composition or a cured product thereof, such that the composition or cured product thereof can be used as described herein. For example, about 0.0001 wt % to about 20 wt % of the composition or cured product thereof can be the one or more surfactants, about 0.001 wt % to about 1 wt %, or about 0.0001 wt % or less, or about 0.001 wt %, 0.005, 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt % or more.

In some embodiments, the surfactant is at least one of a cationic surfactant, an anionic surfactant, and a non-ionic surfactant. In some embodiments, the ionic groups of the surfactant can include counterions, such that the overall charge of the ionic groups is neutral, whereas in other embodiments, no counterion can be present for one or more ionic groups, such that the overall charge of the one or more ionic groups is not neutral.

In one example, the surfactant can be a non-ionic surfactant. Examples of non-ionic surfactants can include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, polyoxyalkylene glycol modified polysiloxane surfactants, and mixtures, copolymers or reaction products thereof. In one example, the surfactant is polyglycol-modified trimethylsilylated silicate surfactant. Examples of suitable non-ionic surfactants can include, but are not limited to, condensates of ethylene oxide with long chain fatty alcohols or fatty acids such as a (C₁₂₋₁₆)alcohol, condensates of ethylene oxide with an amine or an amide, condensation products of ethylene and propylene oxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylol amides, sucrose esters, fluoro-surfactants, fatty amine oxides, polyoxyalkylene alkyl ethers such as polyethylene glycol long chain alkyl ether, polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycol copolymers and alkylpolysaccharides, polymeric surfactants such as polyvinyl alcohol (PVA) and polyvinylmethylether. In certain embodiments, the surfactant is a polyoxyethylene fatty alcohol or mixture of polyoxyethylene fatty alcohols. In other embodiments, the surfactant is an aqueous dispersion of a polyoxyethylene fatty alcohol or mixture of polyoxyethylene fatty alcohols. In some examples, suitable non-ionic surfactants can include at least one of an alkyl polyglycoside, a sorbitan ester, a methyl glucoside ester, an amine ethoxylate, a diamine ethoxylate, a polyglycerol ester, an alkyl ethoxylate, an alcohol that has been at least one of polypropoxylated and polyethoxylated, any derivative thereof, or any combination thereof.

Examples of suitable anionic surfactants can include, but are not limited to, alkyl sulphates such as lauryl sulphate, polymers such as acrylates/C₁₀₋₃₀ alkyl acrylate crosspolymer alkylbenzenesulfonic acids and salts such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid and myristylbenzenesulfonic acid; the sulphate esters of monoalkyl polyoxyethylene ethers; alkylnapthylsulfonic acid; alkali metal sulfoccinates, sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent alcohol esters, amides of amino sulfonic acids, sulfonated products of fatty acid nitriles, sulfonated aromatic hydrocarbons, condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulphates, ester sulphates, and alkarylsulfonates. Anionic surfactants can include alkali metal soaps of higher fatty acids, alkylaryl sulfonates such as sodium dodecyl benzene sulfonate, long chain fatty alcohol sulfates, olefin sulfates and olefin sulfonates, sulfated monoglycerides, sulfated esters, sulfonated ethoxylated alcohols, sulfosuccinates, alkane sulfonates, phosphate esters, alkyl isethionates, alkyl taurates, and alkyl sarcosinates.

Suitable cationic surfactants can include at least one of an arginine methyl ester, an alkanolamine, an alkylenediamide, an alkyl ester sulfonate, an alkyl ether sulfonate, an alkyl ether sulfate, an alkali metal alkyl sulfate, an alkyl or alkylaryl sulfonate, a sulfosuccinate, an alkyl or alkylaryl disulfonate, an alkyl disulfate, an alcohol polypropoxylated or polyethoxylated sulfates, a taurate, an amine oxide, an alkylamine oxide, an ethoxylated amide, an alkoxylated fatty acid, an alkoxylated alcohol, an ethoxylated fatty amine, an ethoxylated alkyl amine, a betaine, a modified betaine, an alkylamidobetaine, a quaternary ammonium compound, any derivative thereof, and any combination thereof. Examples of suitable cationic surfactants can include quaternary ammonium hydroxides such as octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide, tallow trimethyl ammonium hydroxide and coco trimethyl ammonium hydroxide as well as corresponding salts of these materials, fatty amines and fatty acid amides and their derivatives, basic pyridinium compounds, and quaternary ammonium bases of benzimidazolines and poly(ethoxylated/propoxylated) amines.

In some embodiments, the surfactant can be selected from Tergitol™ 15-s-3, Tergitol™ 15-s-40, sorbitan monooleate, polyglycol-modified trimethsilylated silicate, polyglycol-modified siloxanes, polyglycol-modified silicas, ethoxylated quaternary ammonium salt solutions, cetyltrimethylammonium chloride or bromide solutions, an ethoxylated nonyl phenol phosphate ester, and a (C₁₂-C₂₂)alkyl phosphonate. In some examples, the surfactant can be a sulfonate methyl ester, a hydrolyzed keratin, a polyoxyethylene sorbitan monopalmitate, a polyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitan monooleate, a linear alcohol alkoxylate, an alkyl ether sulfate, dodecylbenzene sulfonic acid, a linear nonyl-phenol, dioxane, ethylene oxide, polyethylene glycol, an ethoxylated castor oil, dipalmitoyl-phosphatidylcholine, sodium 4-(1′ heptylnonyl)benzenesulfonate, polyoxyethylene nonyl phenyl ether, sodium dioctyl sulphosuccinate, tetraethyleneglycoldodecylether, sodium octlylbenzenesulfonate, sodium hexadecyl sulfate, sodium laureth sulfate, decylamine oxide, dodecylamine betaine, dodecylamine oxide, N,N,N-trimethyl-1-octadecammonium chloride, xylenesulfonate and salts thereof (e.g., sodium xylene sulfonate), sodium dodecyl sulfate, cetyltrimethylammonium bromide, any derivative thereof, or any combination thereof. The surfactant can be at least one of alkyl propoxy-ethoxysulfonate, alkyl propoxy-ethoxysulfate, alkylaryl-propoxy-ethoxysulfonate, a mixture of an ammonium salt of an alkyl ether sulfate, cocoamidopropyl betaine, cocoamidopropyl dimethylamine oxide, an ethoxylated alcohol ether sulfate, an alkyl or alkene amidopropyl betaine, an alkyl or alkene dimethylamine oxide, an alpha-olefinic sulfonate surfactant, any derivative thereof, and any combination thereof. Suitable surfactants may also include polymeric surfactants, block copolymer surfactants, di-block polymer surfactants, hydrophobically modified surfactants, fluoro-surfactants, and surfactants containing a non-ionic spacer-arm central extension and an ionic or nonionic polar group. In some examples, the non-ionic spacer-arm central extension can be the result of at least one of polypropoxylation and polyethoxylation.

In various embodiments, the surfactant is at least one of a substituted or unsubstituted (C₅-C₅₀)hydrocarbylsulfate salt, a substituted or unsubstituted (C₅-C₅₀)hydrocarbylsulfate (C₁-C₂₀)hydrocarbyl ester wherein the (C₁-C₂₀)hydrocarbyl is substituted or unsubstituted, and a substituted or unsubstituted (C₅-C₅₀)hydrocarbylbisulfate. The surfactant can be at least one of a (C₅-C₂₀)alkylsulfate salt, a (C₅-C₂₀)alkylsulfate (C₁-C₂₀)alkyl ester and a (C₅-C₂₀)alkylbisulfate. In various embodiments the surfactant is a (C₈-C₁₅)alkylsulfate salt, wherein the counterion can be any suitable counterion, such as Na⁺, K⁺, Li⁺, H⁺, Zn⁺, NH₄ ⁺, Ca²⁺, Mg²⁺, Zn²⁺, or Al³⁺. In some embodiments, the surfactant is a (C₈-C₁₅)alkylsulfate salt sodium salt. In some embodiments, the surfactant is sodium dodecyl sulfate.

In various embodiments, the surfactant is a (C₅-C₅₀)hydrocarbyltri((C₁-C₅₀)hydrocarbyl)ammonium salt, wherein each (C₅-C₅₀)hydrocarbyl is independently selected. The counterion can be any suitable counterion, such as Na⁺, K⁺, Li⁺, H⁺, Zn⁺, NH₄ ⁺, Ca²⁻, Mg²⁺, Zn²⁺, or Al³⁺. The surfactant can be a (C₅-C₅₀)alkyltri((C₁-C₂₀)alkyl)ammonium salt, wherein each (C₅-C₅₀)alkyl is independently selected. The surfactant can be a (C₁₀-C₃₀)alkyltri((C₁-C₁₀)alkyl)ammonium halide salt, wherein each (C₁₀-C₃₀)alkyl is independently selected. The surfactant can be cetyltrimethylammonium bromide.

In some embodiments, the composition or a cured product thereof can further include a hydrolyzable ester. The hydrolyzable ester can be any suitable hydrolyzable ester. For example, the hydrolyzable ester can be a C₁-C₅ mono-, di-, tri-, or tetra-alkyl ester of a C₂-C₄₀ mono-, di-, tri-, or tetra-carboxylic acid. The hydrolyzable ester can be at least one of dimethylglutarate, dimethyladipate, dimethylsuccinate, sorbitol, catechol, dimethylthiolate, methyl salicylate, dimethylsalicylate, and tert-butylhydroperoxide. Any suitable wt % of the composition or a cured product thereof can be the hydrolyzable ester, such as about 0.01 wt % to about 20 wt %, or about 0.1 wt % to about 5 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or about 20 wt % or more.

In some embodiments, the composition or a cured product thereof further includes at least one tackifier. The tackifier can be any suitable wt % of the composition or cured product thereof, such as about 0.001 wt % to about 50 wt %, about 0.01 wt % to about 30 wt %, or about 0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or about 50 wt % or more. The tackifier can be any suitable material having tackiness. For example, the tackifier can be an adhesive or a resin. The term “resin” as used herein refers to any of numerous physically similar polymerized synthetics or chemically modified natural resins including thermoplastic materials and thermosetting materials. In some embodiments, the tackifier can be at least one of a shellac, a polyamide, a silyl-modified polyamide, a polyester, a polycarbonate, a polycarbamate, a urethane, a natural resin, an epoxy-based resin, a furan-based resin, a phenolic-based resin, a urea-aldehyde resin, and a phenol/phenol formaldehyde/furfuryl alcohol resin. In some embodiments, the tackifier can be at least one of bisphenol A diglycidyl ether resin, butoxymethyl butyl glycidyl ether resin, bisphenol A-epichlorohydrin resin, and bisphenol F resin. In some embodiments, the tackifier can be at least one of an acrylic acid polymer, an acrylic acid ester polymer, an acrylic acid homopolymer, an acrylic acid ester homopolymer, poly(methyl acrylate), poly(butyl acrylate), poly(2-ethylhexyl acrylate), an acrylic acid ester copolymer, a methacrylic acid derivative polymer, a methacrylic acid homopolymer, a methacrylic acid ester homopolymer, poly(methyl methacrylate), poly(butyl methacrylate), poly(2-ethylhexyl methacrylate), an acrylamidomethylpropane sulfonate polymer or copolymer or derivative thereof, and an acrylic acid/acrylamidomethylpropane sulfonate copolymer. In some embodiments, the tackifier can include at least one of a trimer acid, a fatty acid, a fatty acid-derivative, maleic anhydride, acrylic acid, a polyester, a polycarbonate, a polycarbamate, an aldehyde, formaldehyde, a dialdehyde, glutaraldehyde, a hemiacetal, an aldehyde-releasing compound, a diacid halide, a dihalide, a dichloride, a dibromide, a polyacid anhydride, citric acid, an epoxide, furfuraldehyde, an aldehyde condensate, a silyl-modified polyamide, and a condensation reaction product of a polyacid and a polyamine.

In some embodiments, the tackifier can include an amine-containing polymer. In some embodiments, the tackifier can be hydrophobically-modified. In some embodiments, the tackifier can include at least one of a polyamine (e.g., spermidine and spermine), a polyimine (e.g., poly(ethylene imine) and poly(propylene imine)), a polyamide, poly(2-(N,N-dimethylamino)ethyl methacrylate), poly(2-(N,N-diethylamino)ethyl methacrylate), poly(vinyl imidazole), and a copolymer including monomers of at least one of the foregoing and monomers of at least one non-amine-containing polymer such as of at least one of polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylpyridine, polyacrylic acid, polyacrylate, and polymethacrylate. The hydrophobic modification can be any suitable hydrophobic modification, such as at least one C₄-C₃₀ hydrocarbyl including at least one of a straight chain, a branched chain, an unsaturated C—C bond, an aryl group, and any combination thereof.

In some embodiments, the composition or a cured product thereof can include a curing agent. The second curing agent can be any suitable curing agent. For example, the curing agent can include at least one of an amine, an aromatic amine, an aliphatic amine, a cyclo-aliphatic amine, polyamines, amides, polyamides, piperidine, diethylene tetramine, ethylene diamine, triethylamine, benzyldimethylamine, N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, piperazine, derivatives of piperazine (e.g., aminoethylpiperazine), pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, carbazole, carbazole, phenanthridine, acridine, phenathroline, phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, indoline, isoindoline, quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexa methylene imine, indazole, polyamines, amides, polyamides, 2-ethyl-4-methyl imidazole, 1,1,3-trichlorotrifluoroacetone, and combinations thereof. The curing agent can form any suitable wt % of the composition or a cured product thereof, such as about 0.001 wt % to about 50 wt %, about 0.01 wt % to about 20 wt %, or about 0.001 wt % or less, or about 0.01 wt %, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or about 50 wt % or more.

In some embodiments, the composition or cured product thereof includes one or more viscosifiers. The viscosifier can be any suitable viscosifier. The viscosifier can affect the viscosity of the composition, cured product thereof, or a solvent that contacts the composition or cured product thereof at any suitable time and location. In some embodiments, the viscosifier provides an increased viscosity at least one of before injection into the subterranean formation, at the time of injection into the subterranean formation, during travel through a tubular disposed in a borehole, once the composition reaches a particular subterranean location, or some period of time after the composition reaches a particular subterranean location. In some embodiments, the viscosifier can be about 0.000,1 wt % to about 10 wt % of the composition or a cured product thereof, about 0.004 wt % to about 0.01 wt %, or about 0.000,1 wt % or less, 0.000,5 wt %, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt % or more.

The viscosifier can include at least one of a substituted or unsubstituted polysaccharide, and a substituted or unsubstituted polyalkene (e.g., a polyethylene, wherein the ethylene unit is substituted or unsubstituted, derived from the corresponding substituted or unsubstituted ethene), wherein the polysaccharide or polyalkene is crosslinked or uncrosslinked. The viscosifier can include a polymer including at least one monomer selected from the group consisting of ethylene glycol, acrylamide, vinyl acetate, 2-acrylamidomethylpropane sulfonic acid or its salts, trimethylammoniumethyl acrylate halide, and trimethylammoniumethyl methacrylate halide. The viscosifier can include a crosslinked gel or a crosslinkable gel. The viscosifier can include at least one of a linear polysaccharide, and a poly((C₂-C₁₀)alkene), wherein the (C₂-C₁₀)alkene is substituted or unsubstituted. The viscosifier can include at least one of poly(acrylic acid) or (C₁-C₅)alkyl esters thereof, poly(methacrylic acid) or (C₁-C₅)alkyl esters thereof, poly(vinyl acetate), poly(vinyl alcohol), poly(ethylene glycol), poly(vinyl pyrrolidone), polyacrylamide, poly (hydroxyethyl methacrylate), alginate, chitosan, curdlan, dextran, emulsan, a galactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine, N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran, pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan, xanthan, welan, derivatized starch, tamarind, tragacanth, guar gum, derivatized guar (e.g., hydroxypropyl guar, carboxy methyl guar, or carboxymethyl hydroxypropyl guar), gum ghatti, gum arabic, locust bean gum, and derivatized cellulose (e.g., carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, or methyl hydroxy ethyl cellulose).

In some embodiments, the viscosifier can include at least one of a poly(vinyl alcohol) homopolymer, poly(vinyl alcohol) copolymer, a crosslinked poly(vinyl alcohol) homopolymer, and a crosslinked poly(vinyl alcohol) copolymer. The viscosifier can include a poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymer including at least one of a graft, linear, branched, block, and random copolymer of vinyl alcohol and at least one of a substituted or unsubstitued (C₂-C₅₀)hydrocarbyl having at least one aliphatic unsaturated C—C bond therein, and a substituted or unsubstituted (C₂-C₅₀)alkene. The viscosifier can include a poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymer including at least one of a graft, linear, branched, block, and random copolymer of vinyl alcohol and at least one of vinyl phosphonic acid, vinylidene diphosphonic acid, substituted or unsubstituted 2-acrylamido-2-methylpropanesulfonic acid, a substituted or unsubstituted (C₁-C₂₀)alkenoic acid, propenoic acid, butenoic acid, pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoic acid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid, acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid, vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid, crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and a substituted or unsubstituted (C₁-C₂₀)alkyl ester thereof. The viscosifier can include a poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymer including at least one of a graft, linear, branched, block, and random copolymer of vinyl alcohol and at least one of vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate, vinyl hexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, and vinyl 3-ethylhexanoate, maleic anhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkanoic anhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkenoic anhydride, propenoic acid anhydride, butenoic acid anhydride, pentenoic acid anhydride, hexenoic acid anhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoic acid anhydride, acrylic acid anhydride, fumaric acid anhydride, methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinyl phosphonic acid anhydride, vinylidene diphosphonic acid anhydride, itaconic acid anhydride, crotonic acid anhydride, mesoconic acid anhydride, citraconic acid anhydride, styrene sulfonic acid anhydride, allyl sulfonic acid anhydride, methallyl sulfonic acid anhydride, vinyl sulfonic acid anhydride, and an N—(C₁-C₁₀)alkenyl nitrogen containing substituted or unsubstituted (C₁-C₁₀)heterocycle. The viscosifier can include a poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymer including at least one of a graft, linear, branched, block, and random copolymer that includes a poly(vinylalcohol/acrylamide) copolymer, a poly(vinylalcohol/2-acrylamido-2-methylpropanesulfonic acid) copolymer, a poly (acrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer, or a poly(vinylalcohol/N-vinylpyrrolidone) copolymer. The viscosifier can include a crosslinked poly(vinyl alcohol) homopolymer or copolymer including a crosslinker including at least one of chromium, aluminum, antimony, zirconium, titanium, calcium, boron, iron, silicon, copper, zinc, magnesium, and an ion thereof. The viscosifier can include a crosslinked poly(vinyl alcohol) homopolymer or copolymer including a crosslinker including at least one of an aldehyde, an aldehyde-forming compound, a carboxylic acid or an ester thereof, a sulfonic acid or an ester thereof, a phosphonic acid or an ester thereof, an acid anhydride, and an epihalohydrin.

In various embodiments, the composition or a cured product thereof can include one or more crosslinkers. The crosslinker can be any suitable crosslinker. In some examples, the crosslinker can be incorporated in a crosslinked viscosifier, and in other examples, the crosslinker can crosslink a crosslinkable material (e.g., downhole). The crosslinker can include at least one of chromium, aluminum, antimony, zirconium, titanium, calcium, boron, iron, silicon, copper, zinc, magnesium, and an ion thereof. The crosslinker can include at least one of boric acid, borax, a borate, a (C₁-C₃₀)hydrocarbylboronic acid, a (C₁-C₃₀)hydrocarbyl ester of a (C₁-C₃₀)hydrocarbylboronic acid, a (C₁-C₃₀)hydrocarbylboronic acid-modified polyacrylamide, ferric chloride, disodium octaborate tetrahydrate, sodium metaborate, sodium diborate, sodium tetraborate, disodium tetraborate, a pentaborate, ulexite, colemanite, magnesium oxide, zirconium lactate, zirconium triethanol amine, zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, zirconium diisopropylamine lactate, zirconium glycolate, zirconium triethanol amine glycolate, zirconium lactate glycolate, titanium lactate, titanium malate, titanium citrate, titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, aluminum lactate, and aluminum citrate. In some embodiments, the crosslinker can be a (C₁-C₂₀)alkylenebiacrylamide (e.g., methylenebisacrylamide), a poly((C₁-C₂₀)alkenyl)-substituted mono- or poly-(C₁-C₂₀)alkyl ether (e.g., pentaerythritol allyl ether), and a poly(C₂-C₂₀)alkenylbenzene (e.g., divinylbenzene). In some embodiments, the crosslinker can be at least one of alkyl diacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylol propane triacrylate, ethoxylated trimethylol propane trimethacrylate, ethoxylated glyceryl triacrylate, ethoxylated glyceryl trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglyceryl monoethylene oxide polyacrylate, polyglyceryl polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dimethacrylate. The crosslinker can be about 0.000,01 wt % to about 5 wt % of the composition of a cured product thereof, about 0.001 wt % to about 0.01 wt %, or about 0.000,01 wt % or less, or about 0.000,05 wt %, 0.000,1, 0.000,5, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, or about 5 wt % or more.

In some embodiments, the composition or a cured product thereof can include one or more breakers. The breaker can be any suitable breaker, such that the surrounding fluid (e.g., a fracturing fluid) can be at least partially broken for more complete and more efficient recovery thereof, such as at the conclusion of the hydraulic fracturing treatment. In some embodiments, the breaker can be encapsulated or otherwise formulated to give a delayed-release or a time-release of the breaker, such that the surrounding liquid can remain viscous for a suitable amount of time prior to breaking. The breaker can be any suitable breaker; for example, the breaker can be a compound that includes a Na⁺, K⁺, Li⁺, Zn⁺, NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and an Al³⁺ salt of a chloride, fluoride, bromide, phosphate, or sulfate ion. In some examples, the breaker can be an oxidative breaker or an enzymatic breaker. An oxidative breaker can be at least one of a Na⁺, K⁺, Li⁺, Zn⁺, NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and an Al³⁺ salt of a persulfate, percarbonate, perborate, peroxide, perphosphosphate, permanganate, chlorite, or hyperchlorite ion. An enzymatic breaker can be at least one of an alpha or beta amylase, amyloglucosidase, oligoglucosidase, invertase, maltase, cellulase, hemi-cellulase, and mannanohydrolase. The breaker can be about 0.001 wt % to about 30 wt % of the composition, or about 0.01 wt % to about 5 wt %, or about 0.001 wt % or less, or about 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % or more.

The composition, a cured product thereof, or a mixture including the composition or a cured product thereof, can include any suitable fluid. For example, the fluid can be at least one of crude oil, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, butylglycidyl ether, propylene carbonate, D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester (e.g., a fatty acid methyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxy ethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethyl sulfoxide, dimethyl formamide, a petroleum distillation product of fraction (e.g., diesel, kerosene, napthas, and the like) mineral oil, a hydrocarbon oil, a hydrocarbon including an aromatic carbon-carbon bond (e.g., benzene, toluene), a hydrocarbon including an alpha olefin, xylenes, an ionic liquid, methyl ethyl ketone, an ester of oxalic, maleic or succinic acid, methanol, ethanol, propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), an aliphatic hydrocarbon (e.g., cyclohexanone, hexane), water, brine, produced water, flowback water, brackish water, and sea water. The fluid can form about 0.001 wt % to about 99.999 wt % of the composition, a cured product thereof, or a mixture including the same, or about 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more.

The composition including the epoxide-containing glycerol ester and the hardening agent, or a cured product thereof, can include any suitable downhole fluid. The composition including the epoxide-containing glycerol ester and the hardening agent can be combined with any suitable downhole fluid before, during, or after the placement of the composition in the subterranean formation or the contacting of the composition and the subterranean material. In some examples, the composition including the epoxide-containing glycerol ester and at least two epoxide substituents and the hardening agent is combined with a downhole fluid above the surface, and then the combined composition is placed in a subterranean formation or contacted with a subterranean material. In another example, the composition including the epoxide-containing glycerol ester and the hardening agent is injected into a subterranean formation to combine with a downhole fluid, and the combined composition is contacted with a subterranean material or is considered to be placed in the subterranean formation. In various examples, at least one of prior to, during, and after the placement of the composition in the subterranean formation or contacting of the subterranean material and the composition, the composition is used in the subterranean formation (e.g., downhole), at least one of alone and in combination with other materials, as a fracturing fluid, spotting fluid, clean-up fluid, completion fluid, remedial treatment fluid, abandonment fluid, pill, cementing fluid, packer fluid, or a combination thereof.

In various embodiments, the composition including the epoxide-containing glycerol ester and the hardening agent, a cured product thereof, or a mixture including the same, can include any suitable downhole fluid, such as an aqueous or oil-based fluid including a fracturing fluid, spotting fluid, clean-up fluid, completion fluid, remedial treatment fluid, abandonment fluid, pill, cementing fluid, packer fluid, or a combination thereof. The placement of the composition in the subterranean formation can include contacting the subterranean material and the mixture. Any suitable weight percent of the composition, cured product thereof, or a mixture including the same that is placed in the subterranean formation or contacted with the subterranean material can be the downhole fluid, such as about 0.001 wt % to about 99.999 wt %, about 0.01 wt % to about 99.99 wt %, about 0.1 wt % to about 99.9 wt %, about 20 wt % to about 90 wt %, or about 0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %, or about 99.999 wt %.

In some embodiments, the composition, a cured product thereof, or a mixture including the same can include any suitable amount of any suitable material used in a downhole fluid. For example, the composition or a cured product thereof can include water, saline, aqueous base, acid, oil, organic solvent, synthetic fluid oil phase, aqueous solution, alcohol or polyol, cellulose, starch, alkalinity control agents, acidity control agents, density control agents, density modifiers, emulsifiers, dispersants, polymeric stabilizers, crosslinking agents, polyacrylamide, a polymer or combination of polymers, antioxidants, heat stabilizers, foam control agents, solvents, diluents, plasticizer, filler or inorganic particle, pigment, dye, precipitating agent, rheology modifier, oil-wetting agents, set retarding additives, surfactants, gases, weight reducing additives, heavy-weight additives, lost circulation materials, filtration control additives, salts, fibers, thixotropic additives, breakers, crosslinkers, rheology modifiers, curing accelerators, curing retarders, pH modifiers, chelating agents, scale inhibitors, enzymes, resins, water control materials, oxidizers, markers, Portland cement, pozzolana cement, gypsum cement, high alumina content cement, slag cement, silica cement, fly ash, metakaolin, shale, zeolite, a crystalline silica compound, amorphous silica, hydratable clays, microspheres, pozzolan lime, or a combination thereof. In various embodiments, the composition or a cured product thereof can include one or more additive components such as: thinner additives such as COLDTROL®, ATC®, OMC 2™, and OMC 42™; RHEMOD™, a viscosifier and suspension agent including a modified fatty acid; additives for providing temporary increased viscosity, such as for shipping (e.g., transport to the well site) and for use in sweeps (for example, additives having the trade name TEMPERUS™ (a modified fatty acid) and VIS-PLUS®, a thixotropic viscosifying polymer blend); TAU-MOD™, a viscosifying/suspension agent including an amorphous/fibrous material; additives for filtration control, for example, ADAPTA®, a high temperature high pressure (HTHP) filtration control agent including a crosslinked copolymer; DURATONE® HT, a filtration control agent that includes an organophilic lignite, more particularly organophilic leonardite; THERMO TONE™, a HTHP filtration control agent including a synthetic polymer; BDF™-366, a HTHP filtration control agent; BDF™-454, a HTHP filtration control agent; LIQUITONE™, a polymeric filtration agent and viscosifier; additives for HTHP emulsion stability, for example, FACTANT™, which includes highly concentrated tall oil derivative; emulsifiers such as LE SUPERMUL™ and EZ MUL® NT, polyaminated fatty acid emulsifiers, and FORTI-MUL®; DRIL TREAT®, an oil wetting agent for heavy fluids; BARACARB®, a sized ground marble bridging agent; BAROID®, a ground barium sulfate weighting agent; BAROLIFT®, a hole sweeping agent; SWEEP-WATE®, a sweep weighting agent; BDF-508, a diamine dimer rheology modifier; GELTONE® II organophilic clay; BAROFIBRE™ O for lost circulation management and seepage loss prevention, including a natural cellulose fiber; STEELSEAL®, a resilient graphitic carbon lost circulation material; HYDRO-PLUG®, a hydratable swelling lost circulation material; lime, which can provide alkalinity and can activate certain emulsifiers; and calcium chloride, which can provide salinity. Any suitable proportion of the composition, cured product thereof, or mixture including the composition or cured product thereof can include any optional component listed in this paragraph, such as about 0.001 wt % to about 99.999 wt %, about 0.01 wt % to about 99.99 wt %, about 0.1 wt % to about 99.9 wt %, about 20 to about 90 wt %, or about 0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %, or about 99.999 wt % or more.

A pill is a relatively small quantity (e.g., less than about 500 bbl, or less than about 200 bbl) of drilling fluid used to accomplish a specific task that the regular drilling fluid cannot perform. For example, a pill can be a high-viscosity pill to, for example, help lift cuttings out of a vertical wellbore. In another example, a pill can be a freshwater pill to, for example, dissolve a salt formation. Another example is a pipe-freeing pill to, for example, destroy filter cake and relieve differential sticking forces. In another example, a pill is a lost circulation material pill to, for example, plug a thief zone. A pill can include any component described herein as a component of a downhole fluid.

A cement fluid can include an aqueous mixture of at least one of cement and cement kiln dust. The composition including the epoxide-containing glycerol ester and the hardening agent, or a cured product thereof, can form a useful combination with cement or cement kiln dust. The cement kiln dust can be any suitable cement kiln dust. Cement kiln dust can be formed during the manufacture of cement and can be partially calcined kiln feed that is removed from the gas stream and collected in a dust collector during a manufacturing process. Cement kiln dust can be advantageously utilized in a cost-effective manner since kiln dust is often regarded as a low value waste product of the cement industry. Some embodiments of the cement fluid can include cement kiln dust but no cement, cement kiln dust and cement, or cement but no cement kiln dust. The cement can be any suitable cement. The cement can be a hydraulic cement. A variety of cements can be utilized in accordance with embodiments of the present invention; for example, those including calcium, aluminum, silicon, oxygen, iron, or sulfur, which can set and harden by reaction with water. Suitable cements can include Portland cements, pozzolana cements, gypsum cements, high alumina content cements, slag cements, silica cements, and combinations thereof. In some embodiments, the Portland cements that are suitable for use in embodiments of the present invention are classified as Classes A, C, H, and G cements according to the American Petroleum Institute. A cement can be generally included in the cementing fluid in an amount sufficient to provide the desired compressive strength, density, or cost. In some embodiments, the hydraulic cement can be present in the cementing fluid in an amount in the range of from 0 wt % to about 100 wt %, about 0 wt % to about 95 wt %, about 20 wt % to about 95 wt %, or about 50 wt % to about 90 wt %. A cement kiln dust can be present in an amount of at least about 0.01 wt %, or about 5 wt % to about 80 wt %, or about 10 wt % to about 50 wt %.

Optionally, other additives can be added to a cement or kiln dust-containing composition of embodiments of the present invention as deemed appropriate by one skilled in the art, with the benefit of this disclosure. Any optional ingredient listed in this paragraph can be either present or not present in the composition or a cured product thereof. For example, the composition can include fly ash, metakaolin, shale, zeolite, set retarding additive, surfactant, a gas, accelerators, weight reducing additives, heavy-weight additives, lost circulation materials, filtration control additives, dispersants, and combinations thereof. In some examples, additives can include crystalline silica compounds, amorphous silica, salts, fibers, hydratable clays, microspheres, pozzolan lime, thixotropic additives, combinations thereof, and the like.

System or Apparatus.

In various embodiments, the present invention provides a system. The system can be any suitable system that can use or that can be generated by use of an embodiment of the composition described herein in a subterranean formation, or that can perform or be generated by performance of a method for using the composition described herein. The system can include a composition including the epoxide-containing glycerol ester and the hardening agent. The system can also include a subterranean formation including the composition therein. In some embodiments, the system includes a cured product of a composition including the epoxide-containing glycerol ester and the hardening agent, and a subterranean formation including the composition therein, such as a consolidated proppant, gravel, or sand pack in the subterranean formation that is consolidated with a cured product of the composition. In some embodiments, the composition in the system can also include a downhole fluid, or the system can include a mixture of the composition and downhole fluid. In some embodiments, the system can include a tubular, and a pump configured to pump the composition into the subterranean formation through the tubular.

Various embodiments provide systems and apparatus configured for delivering the composition described herein to a subterranean location and for using the composition therein, such as for a fracturing operation (e.g., pre-pad, pad, slurry, or finishing stages). In various embodiments, the system or apparatus can include a pump fluidly coupled to a tubular (e.g., any suitable type of oilfield pipe, such as pipeline, drill pipe, production tubing, and the like), the tubular containing a composition including the epoxide-containing glycerol ester and the hardening agent.

In some embodiments, the system can include a drillstring disposed in a wellbore, the drillstring including a drill bit at a downhole end of the drillstring. The system can also include an annulus between the drillstring and the wellbore. The system can also include a pump configured to circulate the composition through the drill string, through the drill bit, and back above-surface through the annulus. In some embodiments, the system can include a fluid processing unit configured to process the composition exiting the annulus to generate a cleaned drilling fluid for recirculation through the wellbore.

In various embodiments, the present invention provides an apparatus. The apparatus can be any suitable apparatus that can use or that can be generated by use of the composition or cured product thereof described herein in a subterranean formation, or that can perform or be generated by performance of a method for using the composition or cured product thereof described herein.

The pump can be a high pressure pump in some embodiments. As used herein, the term “high pressure pump” will refer to a pump that is capable of delivering a fluid to a subterranean formation (e.g., downhole) at a pressure of about 1000 psi or greater. A high pressure pump can be used when it is desired to introduce the composition to a subterranean formation at or above a fracture gradient of the subterranean formation, but it can also be used in cases where fracturing is not desired. In some embodiments, the high pressure pump can be capable of fluidly conveying particulate matter, such as proppant particulates, into the subterranean formation. Suitable high pressure pumps will be known to one having ordinary skill in the art and can include floating piston pumps and positive displacement pumps.

In other embodiments, the pump can be a low pressure pump. As used herein, the term “low pressure pump” will refer to a pump that operates at a pressure of about 1000 psi or less. In some embodiments, a low pressure pump can be fluidly coupled to a high pressure pump that is fluidly coupled to the tubular. That is, in such embodiments, the low pressure pump can be configured to convey the composition to the high pressure pump. In such embodiments, the low pressure pump can “step up” the pressure of the composition before it reaches the high pressure pump.

In some embodiments, the systems or apparatuses described herein can further include a mixing tank that is upstream of the pump and in which the composition is formulated. In various embodiments, the pump (e.g., a low pressure pump, a high pressure pump, or a combination thereof) can convey the composition from the mixing tank or other source of the composition to the tubular. In other embodiments, however, the composition can be formulated offsite and transported to a worksite, in which case the composition can be introduced to the tubular via the pump directly from its shipping container (e.g., a truck, a railcar, a barge, or the like) or from a transport pipeline. In either case, the composition can be drawn into the pump, elevated to an appropriate pressure, and then introduced into the tubular for delivery to the subterranean formation.

FIG. 1 shows an illustrative schematic of systems and apparatuses that can deliver embodiments of the compositions of the present invention to a subterranean location, according to one or more embodiments. It should be noted that while FIG. 1 generally depicts a land-based system or apparatus, it is to be recognized that like systems and apparatuses can be operated in subsea locations as well. Embodiments of the present invention can have a different scale than that depicted in FIG. 1. As depicted in FIG. 1, system or apparatus 1 can include mixing tank 10, in which an embodiment of the composition can be formulated. The composition can be conveyed via line 12 to wellhead 14, where the composition enters tubular 16, with tubular 16 extending from wellhead 14 into subterranean formation 18. Upon being ejected from tubular 16, the composition can subsequently penetrate into subterranean formation 18. Pump 20 can be configured to raise the pressure of the composition to a desired degree before its introduction into tubular 16. It is to be recognized that system or apparatus 1 is merely exemplary in nature and various additional components can be present that have not necessarily been depicted in FIG. 1 in the interest of clarity. In some examples, additional components that can be present include supply hoppers, valves, condensers, adapters, joints, gauges, sensors, compressors, pressure controllers, pressure sensors, flow rate controllers, flow rate sensors, temperature sensors, and the like.

Although not depicted in FIG. 1, at least part of the composition can, in some embodiments, flow back to wellhead 14 and exit subterranean formation 18. The composition that flows back can be substantially diminished in the concentration of various components therein. In some embodiments, the composition that has flowed back to wellhead 14 can subsequently be recovered, and in some examples reformulated, and recirculated to subterranean formation 18.

It is also to be recognized that the disclosed composition can also directly or indirectly affect the various downhole or subterranean equipment and tools that can come into contact with the composition during operation. Such equipment and tools can include wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, slickline, wireline, drill pipe, drill collars, mud motors, downhole motors and/or pumps, surface-mounted motors and/or pumps, centralizers, turbolizers, scratchers, floats (e.g., shoes, collars, valves, and the like), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromechanical devices, and the like), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, and the like), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, and the like), control lines (e.g., electrical, fiber optic, hydraulic, and the like), surveillance lines, drill bits and reamers, sensors or distributed sensors, downhole heat exchangers, valves and corresponding actuation devices, tool seals, packers, cement plugs, bridge plugs, and other wellbore isolation devices or components, and the like. Any of these components can be included in the systems and apparatuses generally described above and depicted in FIG. 1.

Composition for Treatment of a Subterranean Formation.

Various embodiments provide a composition for treatment of a subterranean formation. The composition can be any suitable composition that can be used to perform an embodiment of the method for treatment of a subterranean formation described herein. For example, the composition can include the epoxide-containing glycerol ester and the hardening agent. Various embodiments of the present invention provide a cured product of the composition that includes the epoxide-containing glycerol ester and the hardening agent.

In some embodiments, the composition or cured product thereof further includes a downhole fluid. The downhole fluid can be any suitable downhole fluid. In some embodiments, the downhole fluid is a composition for fracturing of a subterranean formation or subterranean material, or a fracturing fluid. The composition can include a proppant or gravel, such as proppant or gravel having a mixture of components including the epoxide-containing glycerol ester and the hardening agent.

Method for Preparing a Composition for Treatment of a Subterranean Formation.

In various embodiments, the present invention provides a method for preparing a composition for treatment of a subterranean formation. The method can be any suitable method that produces an embodiment of the composition described herein. For example, the method can include forming a composition including the epoxide-containing glycerol ester and the hardening agent.

The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present invention. Thus, it should be understood that although the present invention has been specifically disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present invention.

Additional Embodiments

The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

Embodiment 1 provides a method of treating a subterranean formation, the method comprising:

placing in a subterranean formation a composition comprising

-   -   a glycerol ester comprising at least two epoxides; and     -   a hardening agent.

Embodiment 2 provides the method of Embodiment 1, wherein the method further comprises obtaining or providing the composition, wherein the obtaining or providing of the composition occurs above-surface.

Embodiment 3 provides the method of any one of Embodiments 1-2, wherein the method further comprises obtaining or providing the composition, wherein the obtaining or providing of the composition occurs in the subterranean formation.

Embodiment 4 provides the method of any one of Embodiments 1-3, further comprising consolidating particulates in the subterranean formation with a cured product of the composition.

Embodiment 5 provides the method of Embodiment 1-4, further comprising at least partially curing the composition, to form a cured product of the composition.

Embodiment 6 provides the method of Embodiment 5, wherein the curing occurs in the subterranean formation.

Embodiment 7 provides the method of any one of Embodiments 1-6, wherein the composition further comprises at least one of proppant and gravel.

Embodiment 8 provides the method of Embodiment 7, wherein the proppant or gravel is about 1 wt % to about 90 wt % of the composition.

Embodiment 9 provides the method of any one of Embodiments 7-8, wherein the proppant or gravel is about 5 wt % to about 70 wt % of the composition.

Embodiment 10 provides the method of any one of Embodiments 7-9, wherein the composition is at least partially coated on the proppant or gravel.

Embodiment 11 provides the method of any one of Embodiments 1-10, comprising placing the composition in at least one of a fracture and flowpath in the subterranean formation.

Embodiment 12 provides the method of Embodiment 11, wherein the fracture is present in the subterranean formation when the composition is placed in the subterranean formation.

Embodiment 13 provides the method of any one of Embodiments 11-12, wherein the method comprises forming the fracture or flowpath.

Embodiment 14 provides the method of any one of Embodiments 1-13, further comprising fracturing the subterranean formation to form at least one fracture in the subterranean formation.

Embodiment 15 provides the method of any one of Embodiments 1-14, wherein the glycerol ester comprising at least two epoxides is about 0.001 wt % to about 50 wt % of the composition.

Embodiment 16 provides the method of any one of Embodiments 1-15, wherein the glycerol ester comprising at least two epoxides is about 0.01 wt % to about 30 wt % of the composition.

Embodiment 17 provides the method of any one of Embodiments 1-16, wherein the hardening agent is about 0.001 wt % to about 50 wt % of the composition.

Embodiment 18 provides the method of any one of Embodiments 1-17, wherein the hardening agent is about 0.01 wt % to about 30 wt % of the composition.

Embodiment 19 provides the method of any one of Embodiments 1-18, wherein the composition further comprises a carrier liquid.

Embodiment 20 provides the method of any one of Embodiments 1-19, wherein the glycerol ester is at least one of a mono-, di-, or tri-glyceride.

Embodiment 21 provides the method of any one of Embodiments 1-20, wherein the glycerol ester is a fatty acid glycerol ester.

Embodiment 22 provides the method of any one of Embodiments 1-21, wherein the glycerol ester comprising at least two epoxides has the following structure:

wherein

-   -   R¹, R², and R³ are independently chosen from —H, substituted or         unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴,     -   wherein         -   R⁴ at each occurrence is independently             —C(O)—(C₂-C₆₀)hydrocarbyl comprising at least two oxygen             atoms each independently directly attached to two different             adjacent carbon atoms of the (C₂-C₆₀)hydrocarbyl,         -   the (C₁-C₆₀)hydrocarbyl and the (C₂-C₆₀)hydrocarbyl are             independently interrupted by 0, 1, 2, or 3 groups             independently chosen from —O—, —S—, and substituted or             unsubstituted —NH—, and         -   at least one of R¹, R², and R³ is R⁴.

Embodiment 23 provides the method of Embodiment 22, wherein each of R¹, R², and R³ are independently selected from R⁴ and —H.

Embodiment 24 provides the method of any one of Embodiments 22-23, wherein at least two of R¹, R², and R³ are R⁴.

Embodiment 25 provides the method of any one of Embodiments 22-24, wherein each of R¹, R², and R³ is R⁴.

Embodiment 26 provides the method of any one of Embodiments 22-25, wherein

R¹, R², and R³ are independently chosen from —H, substituted or unsubstituted (C₅-C₆₀)alkyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkyl substituted or unsubstituted (C₅-C₆₀)alkenyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkenyl, and R⁴,

the (C₅-C₆₀)alkenyl and the —C(O)—(C₄-C₅₉)alkenyl each independently comprise about 1 to about 29 carbon-carbon double bonds, and

the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenyl each independently comprise about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, and the (C₅-C₆₀)alkenyl.

Embodiment 27 provides the method of any one of Embodiments 22-26, wherein

R⁴ at each occurrence is independently chosen from —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl, and

the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl each independently comprise about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl.

Embodiment 28 provides the method of any one of Embodiments 1-27, wherein the glycerol ester comprising at least two epoxides is an oil comprising at least one epoxidized aliphatic carbon-carbon double bond.

Embodiment 29 provides the method of any one of Embodiments 1-28, wherein the glycerol ester comprising at least two epoxides is an oil that has been epoxided, wherein the oil is chosen from ester chosen from açai oil, almond oil, amaranth oil, apple seed oil, apricot oil, argan oil, avocado oil, babassu oil, beech nut oil, ben oil, bitter gourd oil, black seed oil, blackcurrant seed oil, borage seed oil, borneo tallow nut oil, bottle gourd oil, buffalo gourd oil, butternut squash seed oil, camelina sativa oil, cape chestnut oil, carob pod oil, cashew oil, cocklebur oil, cocoa butter, coconut oil, cohune oil, coriander seed oil, corn oil, cottonseed oil, date seed oil, dika oil, egusi seed oil, evening primrose oil, flaxseed oil, grape seed oil, grapefruit seed oil, hazelnut oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil, linseed oil, macadamia oil, mafura oil, manila oil, meadowfoam seed oil, mongongo nut oil, mustard oil, niger seed oil, okra seed oil, olive oil, orange oil, palm oil, papaya seed oil, peanut oil, pecan oil, pequi oil, perilla seed oil, persimmon seed oil, pili nut oil, pistachio oil, pomegranate seed oil, poppyseed oil, prune kernel oil, pumpkin seed oil, quinoa oil, ramtil oil, rapeseed oil, rice bran oil, royle oil, safflower oil, sapote oil, seje oil, sesame oil, shea butter, soybean oil, sunflower oil, taramira oil, tea seed oil, thistle oil, tigernut oil, tobacco seed oil, tomato seed oil, walnut oil, watermelon seed oil, wheat germ oil, one or more fractions thereof, or a combination thereof.

Embodiment 30 provides the method of any one of Embodiments 1-29, wherein the glycerol ester comprising at least two epoxides is an oil that has been epoxided, wherein the oil is chosen from agarwood oil, allspice oil, almond oil, anise oil, basil oil, bay leaf oil, benzoin oil, bergamot oil, buchu oil, camphor oil, cannabis oil, cassia oil, cedar oil, celery oil, chamomile oil, cinnamon oil, clary sage oil, clove oil, copaiba oil, cumin oil, eucalyptus oil, frankincense oil, galangal oil, geranium oil, ginger oil, grapefruit oil, guava oil, hops oil, hyssop oil, jasmine oil, juniper oil, lavender oil, lemon grass oil, lemon oil, lemongrass oil, lime oil, manuka oil, mandarin orange, marjoram oil, melaleuca oil, myrrh oil, nutmeg oil, orange oil, oregano oil, patchouli oil, peppermint oil, pine oil, rose oil, rosehip oil, rosemary oil, rosewood oil, sage oil, sandalwood oil, sassafras oil, spearmint oil, tangerine oil, tea tree oil, thyme oil, tsuga oil, valerian oil, vanilla oil, wintergreen oil, ylang-ylang oil, one or more fractions thereof, or a combination thereof.

Embodiment 31 provides the method of any one of Embodiments 1-30, wherein the glycerol ester comprising at least two epoxides is an at least partially epoxidized oil chosen from soybean oil and linseed oil.

Embodiment 32 provides the method of any one of Embodiments 1-31, wherein the glycerol ester comprising at least two epoxides is

Embodiment 33 provides the method of any one of Embodiments 1-32, wherein the glycerol ester comprising at least two epoxides is

Embodiment 34 provides the method of any one of Embodiments 1-33, wherein the glycerol ester comprising at least two epoxides has an epoxide equivalent weight of about 50 g/mol to about 1000 g/mol.

Embodiment 35 provides the method of any one of Embodiments 1-34, wherein the glycerol ester comprising at least two epoxides has an epoxide equivalent weight of about 100 g/mol to about 500 g/mol.

Embodiment 36 provides the method of any one of Embodiments 1-35, wherein the hardening agent comprises at least one primary or secondary amine.

Embodiment 37 provides the method of any one of Embodiments 1-36, wherein the hardening agent comprises at least one of an amine, an aromatic amine, an aliphatic amine, a cyclo-aliphatic amine, a polyamine, an amide, and a polyamide.

Embodiment 38 provides the method of any one of Embodiments 1-37, wherein the hardening agent is selected from the group consisting of diethylene tetramine, ethylene diamine, polyethyleneimine, piperidine, triethylamine, benzyldimethylamine, N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, piperazine, aminoethylpiperazine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, carbazole, carbazole, phenanthridine, acridine, phenathroline, phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, indoline, isoindoline, quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole, polyethyleneimine, 2-ethyl-4-methyl imidazole, 1,1,3-trichlorotrifluoroacetone, a substituted or unsubstituted derivative of any one thereof, and combinations thereof.

Embodiment 39 provides the method of any one of Embodiments 1-38, wherein the composition further comprises a silane coupling agent.

Embodiment 40 provides the method of any one of Embodiments 1-39, wherein the composition further comprises a surfactant.

Embodiment 41 provides the method of any one of Embodiments 1-40, wherein the composition further comprises a hydrolyzable ester.

Embodiment 42 provides the method of any one of Embodiments 1-41, wherein the composition further comprises at least one tackifier.

Embodiment 43 provides the method of any one of Embodiments 1-42, wherein the composition further comprises a curing agent.

Embodiment 44 provides the method of any one of Embodiments 1-43, further comprising combining the composition with an aqueous or oil-based fluid comprising a fracturing fluid, spotting fluid, clean-up fluid, completion fluid, remedial treatment fluid, abandonment fluid, pill, cementing fluid, packer fluid, or a combination thereof, to form a mixture, wherein the placing the composition in the subterranean formation comprises placing the mixture in the subterranean formation.

Embodiment 45 provides the method of any one of Embodiments 1-44, wherein at least one of prior to, during, and after the placing of the composition in the subterranean formation, the composition is used in the subterranean formation, at least one of alone and in combination with other materials, as a fracturing fluid, spotting fluid, clean-up fluid, completion fluid, remedial treatment fluid, abandonment fluid, pill, cementing fluid, packer fluid, or a combination thereof.

Embodiment 46 provides the method of any one of Embodiments 1-45, wherein the composition further comprises water, saline, aqueous base, oil, organic solvent, synthetic fluid oil phase, aqueous solution, alcohol or polyol, cellulose, starch, alkalinity control agent, acidity control agent, density control agent, density modifier, emulsifier, dispersant, polymeric stabilizer, crosslinking agent, polyacrylamide, polymer or combination of polymers, antioxidant, heat stabilizer, foam control agent, solvent, diluent, plasticizer, filler or inorganic particle, pigment, dye, precipitating agent, rheology modifier, oil-wetting agent, set retarding additive, surfactant, corrosion inhibitor, gas, weight reducing additive, heavy-weight additive, lost circulation material, filtration control additive, salt, fiber, thixotropic additive, breaker, crosslinker, gas, rheology modifier, curing accelerator, curing retarder, pH modifier, chelating agent, scale inhibitor, enzyme, resin, water control material, polymer, oxidizer, a marker, Portland cement, pozzolana cement, gypsum cement, high alumina content cement, slag cement, silica cement, fly ash, metakaolin, shale, zeolite, a crystalline silica compound, amorphous silica, fibers, a hydratable clay, microspheres, pozzolan lime, or a combination thereof.

Embodiment 47 provides a system for performing the method of any one of Embodiments 1-46, the system comprising:

a tubular disposed in the subterranean formation; and

a pump configured to pump the composition in the subterranean formation through the tubular.

Embodiment 48 provides a method of treating a subterranean formation, the method comprising:

placing in a subterranean formation a composition comprising

-   -   a glycerol ester comprising at least two epoxides having the         structure:

-   -   wherein         -   R¹, R², and R³ are independently chosen from             —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl, and         -   in at least one of R¹, R², and R³, the (C₂-C₆₀)alkyl and the             (C₂-C₆₀)alkenyl each independently comprise about 2 to about             30 oxygen atoms each independently directly bound to two             different adjacent carbon atoms of R¹, R², and R³, the             (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl; and     -   an amine-functional hardening agent.

Embodiment 49 provides a system comprising:

a composition comprising

-   -   a glycerol ester comprising at least two epoxides; and     -   a hardening agent; and

a subterranean formation comprising the composition therein.

Embodiment 50 provides the system of Embodiment 49, further comprising

a tubular disposed in the subterranean formation; and

a pump configured to pump the composition in the subterranean formation through the tubular.

Embodiment 51 provides a composition for treatment of a subterranean formation, the composition comprising:

a glycerol ester comprising at least two epoxides; and

a hardening agent.

Embodiment 52 provides the composition of Embodiment 51, wherein the composition further comprises a downhole fluid.

Embodiment 53 provides a cured product of the composition of any one of Embodiments 51-52.

Embodiment 54 provides a method of preparing a composition for treatment of a subterranean formation, the method comprising:

forming a composition comprising

-   -   a glycerol ester comprising at least two epoxides; and     -   a hardening agent.

Embodiment 55 provides the composition, method, or system of any one or any combination of Embodiments 1-54 optionally configured such that all elements or options recited are available to use or select from. 

What is claimed is:
 1. A method for treating a subterranean formation, comprising: placing a composition into the subterranean formation, the composition consists essentially of: a glycerol ester comprising at least two epoxides; and a hardening agent.
 2. The method of claim 1, further comprising consolidating particulates in the subterranean formation with a cured product of the composition.
 3. The method of claim 1, wherein the composition is at least partially coated on at least one of proppant, gravel, or a combination thereof, and wherein the proppant or gravel is about 5 wt % to about 70 wt % of the composition.
 4. The method of claim 3, further comprising: forming a fracture in the subterranean formation; and placing the composition and the proppant or gravel in the fracture.
 5. The method of claim 1, wherein the hardening agent is about 0.01 wt % to about 30 wt % of the composition.
 6. The method of claim 1, wherein the glycerol ester comprising at least two epoxides has an epoxide equivalent weight of about 100 g/mol to about 500 g/mol.
 7. The method of claim 1, wherein the glycerol ester comprises a fatty acid glycerol ester.
 8. The method of claim 1, wherein the glycerol ester comprising at least two epoxides has the following structure:

wherein: each R¹, R², and R³ is independently selected from the group consisting of —H, substituted or unsubstituted (C₁-C₆₀)hydrocarbyl, and R⁴, wherein: R⁴ at each occurrence is independently —C(O)—(C₂-C₆₀)hydrocarbyl comprising at least two oxygen atoms each independently directly attached to two different adjacent carbon atoms of the (C₂-C₆₀)hydrocarbyl, the (C₁-C₆₀)hydrocarbyl and the (C₂-C₆₀)hydrocarbyl are independently interrupted by 0, 1, 2, or 3 groups independently chosen from —O—, —S—, and substituted or unsubstituted —NH—, and at least one of R¹, R², and R³ is R⁴.
 9. The method of claim 8, wherein each of R¹, R², and R³ are independently selected from R⁴ and —H.
 10. The method of claim 8, wherein at least two of R¹, R², and R³ are R⁴.
 11. The method of claim 8, wherein each of R¹, R², and R³ is R⁴.
 12. The method of claim 8, wherein: R¹, R², and R³ are independently chosen from —H, substituted or unsubstituted (C₅-C₆₀)alkyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkyl substituted or unsubstituted (C₅-C₆₀)alkenyl, substituted or unsubstituted —C(O)—(C₄-C₅₉)alkenyl, and R⁴, the (C₅-C₆₀)alkenyl and the —C(O)—(C₄-C₅₉)alkenyl each independently comprise about 1 to about 29 carbon-carbon double bonds, and the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenyl each independently comprise about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of the (C₅-C₆₀)alkyl, the —C(O)—(C₄-C₅₉)alkyl, the (C₅-C₆₀)alkenyl, and the —C(O)—(C₄-C₅₉)alkenyl.
 13. The method of claim 8, wherein: R⁴ at each occurrence is independently chosen from —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl, and the (C₂-C₆₀)alkyl and the (C₂-C₆₀)alkenyl each independently comprise about 2 to about 30 oxygen atoms each independently directly bound to two different adjacent carbon atoms of the —C(O)—(C₂-C₆₀)alkyl and —C(O)—(C₂-C₆₀)alkenyl.
 14. The method of claim 1, wherein the glycerol ester comprising at least two epoxides is an at least partially epoxidized oil chosen from soybean oil and linseed oil.
 15. The method of claim 1, wherein the glycerol ester comprising at least two epoxides comprises:


16. The method of claim 1, wherein the glycerol ester comprising at least two epoxides comprises:


17. The method of claim 1, wherein the hardening agent is selected from the group consisting of diethylene tetramine, ethylene diamine, polyethyleneimine, piperidine, triethylamine, benzyldimethylamine, N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, piperazine, aminoethylpiperazine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, carbazole, carbazole, phenanthridine, acridine, phenathroline, phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, indoline, isoindoline, quinuclindine, morpholine, azocine, azepine, azepine, 1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole, polyethyleneimine, 2-ethyl-4-methyl imidazole, 1,1,3-trichlorotrifluoroacetone, and any combination thereof.
 18. A system for performing the method of claim 1, the system comprising: a tubular disposed in the subterranean formation; and a pump configured to pump the composition in the subterranean formation through the tubular.
 19. A method for treating a subterranean formation, comprising: placing proppant or gravel coated with a composition into the subterranean formation, the composition consisting essentially of: a glycerol ester; and a hardening agent, wherein the glycerol ester comprises:

or a combination thereof; and forming a fracture in the subterranean formation.
 20. A composition for treatment of a subterranean formation, consisting essentially of: a glycerol ester; and a hardening agent, wherein the glycerol ester comprises:

or a combination thereof. 